High molecular weight products

ABSTRACT

The present invention describes the production of high molecular weight polyhydric alcohols and their derivatives. In particular the urethane reaction products of polyisocyanates and polyhydric alcohols are described.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.26,859, filed Apr. 4, 1979 now U.S. Pat. No. 4,216,343 issued Aug. 5,1980.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to products and processes useful in themanufacture of synthetic resins.

2. Description of the Art Practices

Hydroformylation is basically defined as the addition of a formyl groupthrough the reaction of an unsaturated compound with carbon monoxide andhydrogen. The basic techology for the manufacture of hydroformylatedproducts and consequently their derivatives is amply set outhereinafter. Among the difficulties which must be met in the manufactureof hydroformylated products is the consideration that hydrogen gas, anexplosive, and carbon monoxide, a hazardous material, are utilized inthe process. Hydroformylation processes are also dependent on expensivemetallic catalysts such as carbonyls which have high toxicity and highcost. The conditions for running a hydroformylation reaction alsoinvolve the use of substantial temperature and pressure thusnecessitating costly equipment which must be maintained.

Thus due to the various factors and considerations which go into themanufacture of hydroformylated products and their derivatives it isessential that the reactions individually and cummulatively give highpurity of the desired end product and high yield thereby avoidingexcessive handling of hazardous materials while minimizing the highcapital cost and maintenance of such production facilities.

In the past several attempts have been made to prepare hydroformylatedproducts or similar materials such as is described in U.S. Pat. No.2,437,600 to Gresham et al issued Mar. 9, 1948. The Gresham patentrelates to the synthesis of organic oxygen containing compounds, inparticular aldehydes. U.S. Pat. No. 2,533,276 to McKeever et al issuedDec. 12, 1950 describes ester-acetals obtained with cobalt catalysts.U.S. Pat. No. 2,599,468 to McKeever issued June 3, 1952 describes theprocess of preparing nonadecyl glycols.

U.S. Pat. No. 3,040,090 issued June 19, 1962 to Alderson et al discussesthe reaction of hydrocarbons with aldehydes and higher alcohols inmethanol to prepare organic oxy compounds. The Alderson et al patentsets forth a number of metallic catalysts which may be employed ineffecting the reactions described therein.

In U.S. Pat. No. 3,043,871 issued July 10, 1962 to Buchner et al theproduction of heptadecane-dicarboxylic acid is described. Foreman et alin U.S. Pat. No. 3,227,640 issued Jan. 4, 1966 describes the productionof olefinically unsaturated alcohols which are of use in manufacturingsome of the end products of the present invention. U.S. Pat. No.3,420,898 issued to Van Winkle et al. on Jan. 7, 1969 discusses the useof cobalt complexes with certain phosphine compounds in the productionof primary alcohols with carbon monoxide and hydrogen.

U.S. Pat. No. 3,530,190 issued Sept. 22, 1970 to Olivier discusseshydrocarbonylation of olefins using certain metal salts. The foregoingreference also discusses the recovery of the complexed metal catalyst.In a patent to Ramsden issued Jan. 16, 1973 as U.S. Pat. No. 3,711,560,the production of polyolefins and other oxygenated organic compoundswhich are polyunsaturated is discussed.

In U.S. Pat. No. 3,787,459 issued Jan. 22, 1974 to Frankel a process isdescribed for converting unsaturated vegetable oil into formyl productswhich are subsequently reduced to the corresponding hydroxymethylderivative or oxidized to the corresponding carboxy products. U.S. Pat.No. 3,899,442 issued Aug. 12, 1975 to Freidrich discusses acomplementary system to that of the Frankel patent whereby rhodiumcatalysts are recovered from the spent hydroformylation reactants.Frankel, again in U.S. Pat. No. 3,928,231, issued Dec. 23, 1975discusses a process of preparing carboxy acid products in high yieldswhile minimizing isomerization of the starting unsaturated vegetableoil. Miller et al. in U.S. Pat. No. 4,093,637 issued June 6, 1978discusses the use of formyl stearic acid to prepare bisacyloxymethylstearic acid which is stated to be useful as a plasticizer.

U.S. Pat. No. 3,931,332 issued Jan. 6, 1976 to Wilkes discusseshydroformylation reactions in which the destructive disassociation ofthe catalyst is inhibited by the presence of organic nitrogen compounds.Reichspatentamt Patentschrift No. 745,265 to Mannes et al published Mar.1, 1944 discusses the preparation of dicarboxylic acids and their salts.In Bundesrepublik Deutschland Pat. No. 965 697 issued June 13, 1957 toBlaser and Stein the reaction of unsaturated alcohols and theirderivatives with metal carbonyls and carbon monoxide is discussed. Aby-product which is obtained through the technology of Blaser et alincludes substantial amounts of monoformylated product. Similarly aformylation technique which results in a monoformylated product whenusing unsaturated alcohols is discussed in an article by Ucciani et alin the Bull. Soc. Chim. (France) 1969 p. 2826-2830. SimilarlyBundesrepublik Pat. No. 1,054,444 published Apr. 9, 1959 to Waldmann andStein discusses the treatment of unsaturated fatty substances withformaldehyde in the presence of a carboxylic anhydride and an acidiccatalyst to provide formyl products.

Substantial work has been done on the production of varioushydroformylated products by the United States Department of Agricultureat both the Eastern and Western Regional Research Laboratories. Forexample, in an article by Roe entitled "Branched Carboxylic Acids fromLong-Chain Unsaturated Compounds and Carbon Monoxide at AtmosphericPressure" published at J. Am. Oil Chemists' Soc. 37, p. 661-668 (1960).The production by direct carboxylation at atmospheric pressure ofunsaturated acids with carbon monoxide or formic acid is discussed. Thehydroformylation of unsaturated fatty esters is discussed by Frankel etal at J. Am. Oil Chemists' Soc. 46, p. 113-138 (1968). Frankel has alsoreported a selective catalyst system for the hydroformylation of methyloleate utilizing rhodium catalyst in the presence of triphenylphosphinein an article entitled "Methyl 9(10)-Formylstearate by SelectiveHydroformylation of Oleic Oils" at J. Am. Oil Chemists' Soc. 48, p.248-253 (1971).

In a paper presented at the American Oil Chemists' Society meeting inAtlantic City, N.J. in 1971, Dufek et al discusses the esterificationand transesterification of dicarboxylic acids under the title"Esterification and Transesterification of 9(10)-Carboxystearic Acid andIts Methyl Esters". The foregoing article was published at J. Am. OilChemists' Soc. 49 (5) p. 302-306 (1972). Frankel, again, discusses theuse of specific catalysts to obtain hydroformylated products in anarticle titled "Selective Hydroformylation of Polyunsaturated Fats Witha Rhodium-Triphenylphosphine Catalyst", J. Am. Oil Chemists' Soc. 49, p.10-14 (1972). Freidrich at Vol. 17, No. 3 of Ind. Eng. Chem. Prod. Res.Dev. (1978) presents an article entitled "Low-Pressure Hydroformylationof Methyl-Oleate With an Activated Rhodium Catalyst".

Pryde, working with Frankel and Cowan discuss hydroformylation via theoxo reaction, Koch carboxylation and Reppe carbonylation in an articleentitled "Reactions of Carbon Monoxide with Unsaturated Fatty Acids andDerivatives: A Review", reported at J. Am. Oil Chemists' Soc. 49, p.451-456 (1972).

Friedrich discusses the hydroformylation of unsaturated esters combinedwith catalyst recovery in an article entitled "Hydroformylation ofMethyl Oleate with a Recycled Rhodium Catalyst and Estimated Costs for aBatch Process" at J. Am. Oil Chemists' Soc. 50, p. 455-458 (1973). Asimilar area of technology is also reported by Frankel et al in anarticle entitled "Hydroformylation of Methyl Linoleate and Linolenatewith Rhodium-Triphenylphosphine Catalyst" from I&EC Product Research &Development, Vol. 12, p. 47-53 (1973).

Certain condensation polymers prepared from pentaerythritol acetalderivatives are reported in an article "Poly(Amide-Acetals) andPoly(Ester-Acetals) from Polyol Acetals of Methyl (9(10)-Formylstearate:Preparation and Physical Characterization" reported at J. Am. OilChemist' Soc. 53, p. 20-26 (1976). Compounds obtained throughhydroformylation technology useful as plasticizers are discussed in aFrankel et al article entitled "Acyl Esters from Oxo-DerivedHydroxymethylstearates as Plasticizers for Polyvinyl Chloride" printedin the J. Am. Oil Chemists' Soc. 52, p. 498-504 (1975).

Friedrich in an article entitled "Oxidation of Methyl Formylstearatewith Molecular Oxygen" at J. Am. Oil Chemists' Soc. 53, p. 125-129(1976) reports the use of air or oxygen to form methyl carboxystearatefrom methyl formylstearate in an emulsion with a soluble rhodiumcomplex. The reuse of catalyst in hydroformylation reactions isdescribed by Awl in an article entitled "Hydroformylation with RecycledRhodium Catalyst and One-Step Esterification-Acetalation: A Process forMethyl 9(10)-Methoxymethylenestearate from Olefic Acid" which is printedin J. Am. Oil Chemists' Soc. 53, p. 190-195 (1976).

Useful diols for resin purposes are described in U.S. Pat. No. 2,933,477issued Apr. 19, 1960 to Hostettler. Nonadecanediols are described asbeing utilized in urethane formulations in U.S. Pat. No. 3,243,414 toDeWitt et al issued Mar. 29, 1966. The production of triols which arenot particularly useful in resins due to the close positioning of thehydroxyl groups is reported in Improved Synthesis of1,1,1-trimethylolalkanes from Hexanal and Nonanal J. Am. Oil Chemists'Soc. 45, p. 517 (July 1968) by Moore and Pryde.

Frankel et al in a paper entitled Catalytic Hydroformylation andHydrocarboxylation of Unsaturated Fatty Compounds at J. Am. OilChemists' Soc. 54, p. 873A (1977) also describes formylation technology.Frankel also describes the use of carbonyl metallic compounds inhydroformylations in an article entitled "Catalytic Hydroformylation ofUnsaturated Fatty Derivatives with Cobalt Carbonyl" at J. Am. OilChemists' Soc. 53, p. 138-141 (1976). The use of esters of variouscarboxystearic acids is discussed by Dufek et al in an article entitled"Some Esters of Mono-, Di-, and Tricarboxystearic Acid as Plasticizers:Preparation and Evaluation" at J. Am. Oil Chemists' Soc. 53, p. 198-203(1976). Dufek et al also report catalyst recovery in an article entitled"Recovery of Solubilized Rhodium from Hydroformylated Vegetable Oils andTheir Methyl Esters" in J. Am. Oil Chemists' Soc. 54, p. 276-278.

Frankel discusses hydroformylation generally in an article entitledSelective Hydroformylation of Unsaturated Fatty Acid Esters at AnnalsN.Y. Academy of Sciences 214:79 (1973). Catalyst technology is reviewedat Recent Developments in Hydroformylation Catalysts in Catal. Rev. 6(1) page 49 et seq. (1972).

Defek alone at J. Am. Oil Chemists' Soc. 55, p. 337-339 (1978) reportson the conversion of methyl 9(10) formylstearate in an article entitled"Conversion of Methyl 9(10)-Formylstearate to Carboxymethylstearate".

Acetal esters obtainable through hydroformylation technology arereported by Adlof et al in an article entitled "Preparation andSelective Hydrolysis of Acetal Esters" at J. Am. Oil Chemists' Soc. 54,p. 414-416 (1977). Selective catalyst systems are again reported byFrankel in the J. Am. Oil Chemists' Soc. 54, p. 873a-881a (1977) in anarticle entitled "Catalytic Hydroformylation and Hydrocarboxylation ofUnsaturated Fatty Compounds".

The plasticization of polyvinylchloride resins is also reported inpatent applications and coded P.C. 6333 and 6375 bearing respectivelythe titles "Acetoxymethyl Derivatives of Polyunsaturated FattyTriglycerides as Primary Plasticizers for Polyvinylchloride", and "Alkyl9,9(10,10)-Bis(acyloxymethyl) octadecanoates as Primary Plasticizers forPolyvinylchloride".

Each of the foregoing to the extent that it is applicable to the presentinvention is herein incorporated by reference.

The basic purpose of the present invention is to describe as endproducts the preparation of high molecular weight polyhydric alcoholsand their useful urethane reaction products formed by the condensationof the polyhydric alcohol with a polyisocyanate. Of course several otheruses of the technology embodied in this patent are readily apparent.

Throughout the specification and claims of the present inventionpercentages and ratios are by weight and temperatures are in degrees ofCelsius unless otherwise indicated.

SUMMARY OF THE INVENTION

The present invention describes a mixture of a diol (a) and a alcohol(b) of the formula:

(a) H(CH₂)_(h) CH(CH₂ OH) (CH₂)_(k) CH₂ OH

and

(b) CH₃ (CH₂)_(m) [C(CH₂ OH)₂ ]_(n) (CH₂)_(p) [C(CH₂ OH)₂ ]_(q)(CH₂)_(r) [C(CH₂ OH)₂ ]_(s) (CH₂)_(t) CH₂ OH

and mixtures thereof wherein n plus q plus s are integers the sum ofwhich is from 1 to 3; k and t are 3 or greater; n, q, and s are 0 or 1;m through t are integers the sum of which is from 12 to 20; and, h plusk are non-zero integers the sum of which is from 12 through 20.

DETAILED DESCRIPTION OF THE INVENTION

The products of the present invention are formed throughhydroformylation which is the process for the production of aldehydesfrom olefinically unsaturated compounds by reaction with carbon monoxideand hydrogen in the presence of a catalyst. The aldehydes producedgenerally correspond to the compounds obtained by the addition of ahydrogen and a formyl group to an olefinicably unsaturated group in thestarting material thus saturating the olefinic bond.

The useful products of the present invention are prepared byhydroformylating an unsaturated alcohol of the formula

    H(CH.sub.2).sub.a (CH═CH).sub.b (CH.sub.2).sub.c (CH═CH).sub.d (CH.sub.2).sub.e (CH═CH).sub.f (CH.sub.2).sub.g CH.sub.2 OH

where hereinafter (1) a and g are not equal to 0; (2) the integers bplus d plus f are equal to y which has a value of from 1 to 3; (3) thesum of the integers a plus c plus e plus g is equal to x; and (4) x plus2y is equal to from 13 to 21.

In the polyol (5) m through t are integers the sum of which is from 12through 20; (6) n plus q plus s are 1 through 3, and; (7) n, q, and sare 0 or 1, preferably such that the sum of m through t is from 14 to 18and x plus 2y is 15 to 19; and (8) m, h, k and t are each 3 or greater.A second preferred embodiment is where n, p, r, and s are 0 and m plus tis 11 through 19.

It is particularly preferred that h plus k are non-zero integers the sumof which is from 12 to 20, preferably 14 to 18 and where m, h, k and tare 4, 5 or 6 or greater. It is also preferred that q is 1 and n and sare each 0.

Most preferably the starting raw material is oleyl alcohol althoughlinoleyl or linolenyl alcohol may be employed. It is of course notedthat any number of synthetic unsaturated alcohols may also be employedin the present invention. However, for most purposes the naturallyoccurring alcohols derived from plant sources are presently mostconvenient and inexpensive.

The unsaturated alcohol is reacted with hydrogen gas and carbon monoxidein the presence of a rhodium catalyst as later described to form thecorresponding formyl alcohol having the formula

    CH.sub.3 (CH.sub.2).sub.m [CH(CHO)].sub.n (CH.sub.2).sub.p [CH(CHO)].sub.q (CH.sub.2).sub.r [CH(CHO)].sub.s (CH.sub.2).sub.t CH.sub.2 OH

wherein the various subscript numbers are as previously described.

The addition of hydrogen and carbon monoxide is accomplished in practiceby conveniently adding stoichiometric amounts of the hydrogen and carbonmonoxide to give the formyl alcohol. To assure completeness of thereaction the amounts of hydrogen and carbon monoxide may be eachmaintained at from about 1.5:0.5 to about 0.5:1.5 molar ratio to oneanother. It is noted that the ratio is not critical as long as thepressure is maintained in the reaction vessel by the component gases andthat the amount of hydrogen is not so great as to substantially reducethe unsaturated starting material.

The rhodium catalyst as later described is necessary in thehydroformylation reaction in that it has been found that the use of themore conventional cobalt catalyst results in a substantial amount ofcross-linking gelation. It is believed that the gelation is due to thecoproduction of polyhemiacetals and polacetals in competition with theproduction of the hydroformylated alcohol. It was at first believed bythe author that it would be necessary, even with a rhodium catalyst, toemploy the ester of the unsaturated alcohol e.g. oleyl acetate to avoidthe unwanted by-products. Of course the ester is more expensive andeventually is converted to the alcohol in any event.

Higher yields of product are obtained through the use of the rhodiumcatalysts than if a cobalt catalyst is employed. It has also beenobserved that a much higher degree of isomerization of the double bondoccurs with a cobalt catalyst than with a rhodium catalyst.

The conditions for pressure and temperature during the hydroformylationare conveniently conducted at from about 90 degrees C. to about 170degrees C., preferably from about 110 degrees C. to about 130 degrees C.Above the higher temperatures listed above increased amounts of unwantedbyproducts are formed in the reaction mixture. The pressure conditionsare such that the pressure in the sealed system is maintained at fromabout 20 to about 500 atmospheres, preferably from about 30 to about 100atmospheres absolute during the hydroformylation.

The preferred end product obtained from conducting the foregoing processis 9(10) formyl octadecanol when the starting material is oleyl alcohol.The positioning of the 9(10) indicates that the product obtained is amixture of the 9 and 10 isomer with respect to the formyl group. Oneadditional reason for using a rhodium catalyst is that if a cobaltcatalyst were employed a considerable amount of terminal aldehyde wouldbe formed due to bond migration prior to the addition of the formylgroup. When the terminal aldehyde group is formed the resultant alcoholobtained by carrying out the remainder of the herein described processis unsuitable for many of the purposes that the geminal alcohols may beutilized for.

It should also be appreciated that if 9,12-linoleyl alcohol is thestarting material then the formyl alcohol so formed will be a 9(10),12(13) diformyloctadecanol. That is, the end product obtained here willactually be a mixture of the 9-12,9-13,10-12,10-13 diformyl alcohols.Similarly without discussing all the particular isomers present when9,12,15-linolenyl alcohol is employed the product so obtained will be amixture of the 9(10), 12(13), 15(16) triformyloctadecanol isomers.

It is particularly important that the expensive rhodium catalyst isrecovered. This may be conveniently done by distillation of the formylalcohol leaving the rhodium in the residue. What is particularlysurprising is that the rhodium can be recovered from the distillate inthat the art would predict that when hydroformylating an unsaturatedalcohol that the products obtained would include considerable quantitiesof polyhemiacetals and polyacetals as a portion or all of the reactionproduct and that these products would not be recoverable bydistillation. Thus not only is the desired end product achieved in ahigh degree of purity and yield through the use of the rhodium catalystbut the rhodium catalyst is recoverable in extremely high quantitiesfrom the reaction mixture.

It should also be emphasized that if the polyhemiacetals and polyketalswere formed in the reaction mixture that it is very likely that thereaction components would undergo a great change in viscosity to thepoint of forming a semi-solid product due to the extensive cross-linkingof the acetal and ketal linkages. Thus a substantial reason exists foravoiding the polyhemiacetal and polyacetal formation through the use ofa rhodium catalyst.

It may be stated that the polyacetal and polyhemiacetal formation mightbe prevented by the utilization of the corresponding unsaturated acid orits ester in place of the unsaturated alcohol. However, thissubstitution which eventually involves the acid ester is undesirable inthat an aqueous neutralization step is required which forms a soap as abyproduct. The soap so formed then emulsifies the reaction products andthe water present to make separation extremely difficult thusdiminishing recovery of both the alcohol and the expensive catalyst.Thus the present invention is highly selective to both the unsaturatedalcohol and the particular rhodium catalyst so employed.

Any convenient source of rhodium may be employed as in the presentreaction mixture the rhodium catalyst is actually converted through thepresence of the hydrogen and carbon monoxide into its active form whichis a rhodium carbonyl hydride. Conveniently the source of rhodium foruse in the rhodium catalyst may be rhodium metal, rhodium oxide, andvarious other rhodium salts such as rhodium chloride, rhodium dicarbonylchloride dimer, rhodium nitrate, rhodium trichloride and other similarmaterials.

The rhodium catalyst in the present hydroformylation reaction ispreferably present with a ligand such as a trisubstituted phosphine ortrisubstituted phosphite. The term trisubstituted includes both alkyland aryl compounds and the substituted compounds of the alkyl and arylcompounds. A particularly valuable ligand for the rhodium carbonylhydride is triphenylphosphite or triphenylphosphine in that bothcompounds are particularly useful in minimizing migration of the doublebond thereby avoiding a large number of isomers with respect to theformyl group including the undesired terminal formyl compound aspreviously discussed. In general triaryl phosphines or triarylphosphitesmay be used for this purpose in the formation of the rhodium carbonylhydride ligand. In addition, the foregoing materials are extremelyvaluable in minimizing the undesired reaction of saturation of thedouble bond or the reduction formyl group. This frequently occurs in theabsence of such ligands because the rhodium catalyst functionsexcellently as a hydrogenation catalyst. That is the ligand tends toeliminate such side reactions.

In general anyone of several other additional ligands may be used withthe rhodium catalyst. Such additional ligands are discussed in theSelective Hydroformylation of Unsaturated Fatty Acid Esters by Frankelin the Annals N.Y. Academy of Sciences 214:79 (1973).

The various ligands are conveniently employed in mole ratio to therhodium metal content of the catalyst of from about 2 to 50 preferablyfrom about 3 to 20. The rhodium catalyst based upon its metal content isconveniently employed in catalytic amounts preferably from about 22 ppmto about 10,000 ppm, most preferably from about 50 ppm to about 500 ppmby weight of the unsaturated alcohol.

The various formyl alcohols are useful as previously stated in preparingthe highly desired gem-bis(hydroxymethyl) alcohols. The alcohols may beformed from the foregoing formyl alcohols via a Tollens' reaction (aldolcondensation followed by a crossed-Cannizzaro reaction).

Schematically the Tollens' reaction is as described below. ##EQU1##wherein the above formula R indicates an organic moiety, compound (I) isa hydroxymethyl aldehyde and MOH is a strong base.

The Tollens' reaction is thus carried out by reacting one mole of amonoformylated alcohol with two moles of formaldehyde in an inertatmosphere such as nitrogen. Where the formyl alcohol contains more thanone formyl group, two moles of formaldehydes are required for eachformyl group present. Thus if the reactant is formyloctadecanol then twomoles of formaldehyde are required for conversion to thegem-bis(hydroxymethyl) alcohol whereas if linolcyl alcohol is utilizedin the first instance to give a diformyloctadecanol then four moles offormaldehyde are required to obtain the di-geminaloctadecanol.Conveniently an excess of up to 1.5 preferably up to 1.2 times theamount of formaldehyde actually required to form the correspondinggem-bis(hydroxymethyl) alcohol is employed in the present invention. Aconvenient matter of adding the formaldehyde in the Tollens' reaction isby using a methanol solution of formaldehyde.

The Tollens' reaction utilizes a strong base as both a reactant and acatalyst. Such strong bases include sodium, potassium or calciumhydroxide. Other strong bases such as carbonates or other hydroxides maybe used as well. The strong base is conveniently employed on anequivalent basis per formyl group to convert the formyl group to thehydroxy methyl group. The amount of base required in the Tollens'reaction is at least an equivalent of that required preferably up to1.5, most preferably up to 1.2 equivalents. The Tollens' reaction isconducted at a temperature of from about 0 degrees C. to about 100degrees C., preferably from about 20 degrees C. to about 70 degrees C.

The crude gem-bis(hydroxymethyl) alcohol so formed is washed with waterto remove any excess caustic and salts formed and then obtained in arelatively pure state by vacuum drying.

In obtaining the gem-bis(hydroxymethyl) alcohol of the present inventionthe crossed-Cannizzaro reaction predominates over the rate of reactionfor the simple Cannizzaro reaction. The Cannizzaro reaction which ispromoted by base, water, and heat is the process by which an aldehydereacts with itself to form the corresponding alcohol and formate salt.That is, in the present invention the formyl group on the formyl alcoholreacts faster with formaldehyde to give the alcohol than does theformaldehyde react with itself.

It is also surprising that the formation of hemiacetal which may be acidor base catalyzed does not occur upon the addition of base to the formylalcohol while forming the intermediate hydroxymethyl formyl alcohol.Thus two potential side reactions, the Cannizzaro and the hemiacetalformation (and thereafter the acetal) which might be expected given thereactants and the processing conditions involved do not in fact occurand the useful alcohol is obtained in substantial quantities.

It has been found, however, in the present invention that the morecomplicated crossed-Cannizzaro surprisingly predominates in rate andamount of product (gem-bis(hydroxymethyl) alcohol) produced despite thesteric hinderance of the larger formyl alcohol molecule even underconditions which are known to promote the simple Cannizzaro reaction.

An alternative method of accomplishing the formation of the geminalalcohol is to use only about one-half the equivalent amount of theformaldehyde required in the Tollens' reaction thereby forming thecorresponding hydroxymethyl formyl alcohol via the aldol condensation.That is, the hydroxymethyl group is attached to the carbon in the alphaposition to the formyl group. Where a polyformyl alcohol is theintermediate product the formaldehyde is halved from that utilized inthe Tollens' reaction to give the corresponding polyhydroxymethylpolyformyl alcohol.

This variation of forming the geminal alcohol eliminates the need forthe strong base required in the Tollens' reaction and utilizes insteadonly catalytic amounts of base which may be either a weak or strongbase. A preferred weak base is triethylamine. Even here some care mustbe taken as it is possible even when using a weak base to obtaincompound (I) as the Cannizzaro reaction may compete with the aldolcondensation.

The hydroxymethyl formyl alcohol so formed by this alternative route isthen reduced to the alcohol conveniently by using hydrogen gas and asuitable hydrogenation catalyst such as copper chromite, or nickel, viaconventional hydrogenation practice or by lithium aluminum hydrideproduction. A significant advantage to the alternative route is theabsence of large amounts of salt and solvents needed in the Tollens'reaction route.

A distinct advantage in the geminal alcohol of the present invention isthat it is a liquid at room temperature and further has no tertiaryhydrogens which are a weak point for chemical attack on the molecule.

A mixture of the diol and the geminal alcohol is obtained by reactingthe unsaturated alcohol to obtain the corresponding formyl alcohol.Thereafter the formyl alcohol is split into two streams, the first ofwhich is processed as previously discussed to give the geminal alcoholwhile the second stream is reduced by hydrogenation to give the diol.The hydrogenation is generally carried out as discussed in thealternative route for preparing the geminal alcohol. The diol and thegeminal alcohol are then recombined in the desired proportions which arepreferably in a weight ratio of from about 2:1 to about 1:100 morepreferably from about 1:1 to about 1:75. The preferred value for the sumof h and k is from 14 to 18. The liquid nature of the geminal alcoholaids in solubilizing the normally solid diol thus giving a product whichis easy to compound.

The products of the present invention are useful in preparingpolyurethanes. Among the products which may be obtained from thealcohols are rigid foams and thermosetting elastomers. Additional usesof the gem-bis(hydroxymethyl) alcohols of the present invention includescalants, polyvinyl alcohol plasticizers, and poly(oxy)alkylene adductssuch as ethylene and propylene oxide adducts for polyurethanes ordetergents. The poly(oxy)alkylenes and their halogenated derivatives(especially chlorinated) are particularily useful in polyurethanes. Thealcohols formed in the present invention may be reacted with an anionicspecies to give surfactant products such as the sulfated reactionproducts of the alcohol. Additional surfactants may be formed by firstadducting the alcohol with a poly(oxy)alkylene such as ethylene orpropylene oxide and then adding the sulfate group. The present inventionalso contemplates the caprolactone adducts of the alcohols.

Further uses of the present invention include microcellular foams, thereaction of the alcohol with materials such as acrylic or methacrylicacids to give radiation curable coatings. The alcohols of the presentinvention may also be used as lubricants or oil substitutes. A furtheruse of the present alcohol compounds are their formation into glycidylethers and their subsequent use as a new type of epoxy coating. Afurther use of the geminal alcohol is in cosmetic preparationsparticularly as an emollient.

The primary aspect of the present invention, however, is the use of thealcohols so formed as reaction products with isocyanates to formpolyurethanes. To form the urethane reaction product of the alcohol areaction is conducted which requires the presence of an organicpolyisocyanate compound.

Suitable polyisocyanates include ethylene diisocyanate, trimethylene,diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate,ethylidene diisocyanate, cyclopentylene-1,3-diisocyanate, the 1,2-,1,3-and 1,4-cyclohexylene diisocyanates, the 1,3- and 1,4-phenylenediisocyanates, polymethylene polyphenylene-isocyanates, the 2,4- and2,6- toluene diisocyanates, the 1,3- and 1,4-xylylene diisocyanates,bis(4-isocyanatophenyl) methane, 4,4'-diphenyl-propane diisocyanates,bis(2-isocyanatoethyl) carbonate, 1,8-diisocyanato-p-methane,1-methyl-2,4-diisocyanato-cyclohexane, the chlorophenylenediisocyanates, naphthalene-1,5-diisocyanate triphenylmethane-4,4',triisocyanate, isopropylbenzene-alpha-4-diisocyanate,5,6-bicyclo[2.2.1]hept-2-ene diisocyanate,5,6-diisocyanatobutylbicyclo[2.2.1]hept-2-ene and similarpolyisocyanates.

Of particular interest in the present invention are trimethylenehexamethyl diisocyanate available from VEBA, heptadecyl (C17)diisocyanate, DDI 1410 an aliphatic C-36 diisocyanate available from theHenkel Corporation of Minneapolis, Minn. (Generally diisocyanates havingfrom 12 to 40 carbons in the aliphatic radical may be used in thepresent invention), toluene diisocyanate available from Allied Chemical,isophorone diisocyanate available from VEBA and Desmodur N. an aliphatictriisocyanate available from Mobay. Desmodur N is more particularlydefined the tri-isocyanate adduct of 3 moles of hexamethylenediisocyanate and water having an isocyanate equivalent weight as laterdefined of 191 grams. Other adducts or prepolymers of the polyisocyanateinclude Desmodur L and Mondur CB which are the adducts of foluenediisocyanate. The foregoing materials have an isocyanate equivalentweight of approximately 250 grams.

The amount of the polyisocyanate utilized in forming the urethanecompositions of the present invention is expressed on a percentageequivalent weight basis with respect to the hydroxyl functionality ofthe alcohol. Desirably each hydroxy functional group on the alcohol willreact on a 1:1 stoichiometric basis with the isocyanate functionality onthe polyisocyanate compound. It is quite feasible, however, to form theurethane linkage using from about 80% to 120% preferably from about 95%to 105% on a hydroxyl-isocyanate equivalent basis of the polyisocyanateto form the urethane product.

To determine the amount of the polyisocyanate required for a givensaturated polyol the hydroxyl or isocyanate equivalent weight of therespective polyol or polyisocyanate is determined as that weight ingrams of the material which contains 1 gram equivalent weight of therespective functional group. More particularly to determine the numberof equivalents in a given saturated polyol the hydroxyl value is firstdetermined by known methods and reported in milligrams of potassiumhydroxide. The calculation to determine the hydroxyl equivalents is thengiven by the following equation: ##EQU2## where 56,100 is the milligramequivalent weight of potassium hydroxide.

Alternatively if the weight percentage of the hydroxyl groups in thesaturated polyol is known the hydroxyl equivalent is determined asfollows: ##EQU3## where 17 is the equivalent weight of the hydroxylradical and the weight percent OH is the percentage of the saturatedpolyol which is hydroxyl groups.

In similar fashion the isocyanate equivalent may be determined if theweight percent of the isocyanate functional groups in the polyisocyanateis known. This equation is given below where 42 is the molecular weightof an isocyanate functional group and the weight percent NCO is thatportion of polyisocyanate made up of isocyanate functional groups.##EQU4##

To form the urethane reaction product the alcohol of the presentinvention and the organic polyisocyanate are merely mixed together inthe proper proportions. When utilized as a coating the compounds arethen quickly spread with a knife blade brush or spray over the surfaceof the article to be coated. Where molded articles are desired varioustechniques such as reaction injection molding. Specific techniques forforming urethane reaction products are hereinafter described in theexamples.

If desired various urethane catalysts may be employed to promote thereaction. Examples of such urethane catalysts include triethylenediamine, morpholine, N-ethyl-morpholine; dimethyl piperazine,triethylamine, N,N,N',N'-tetramethylbutane-1,3diamine, dibutyltindilaurate, stannous octoate, stannous laurate, dioctyltin diacetate,lead octoate, stannous oleate, stannous tallate, dibutyltin oxide, andhexabutylditin as well as other art recognized urethane catalysts.Typical levels of the urethane catalysts are from about 0.001% to about5% by weight of the urethane linking components.

An additional polyol may be included with the alcohols of the presentinvention. Such polyols may be an alkyl or cycloalkyl polyol, an esterlinked polyol, an ether linked polyol, an ether and ester linked polyolor hydroxy functional acrylic copolymers.

Specific examples of alkyl and cycloalkyl polyols include 2,5-hexanediolavailable from Aldrich Chemical, 1,6-hexanediol, available from CelaneseChemical, ethylene glycol available from Baker, Dimerol a 36 carbonessentially linear diol available from General Mills Chemicals, Inc.,glycerol, 1,2-6-hexanetriol available from Union Carbide,pentaerythritol, and 1,4-cyclohexane diol. Additional examples of suchpolyols include Polybd R-45HT a Butadiene diol having an approximatemolecular weight of 2800 available from Arco and Trimethylol propaneavailable from Celanese.

The ester linked saturated diols of the present invention are moreparticularly described as polyols where the predominate linkage(functional group other than the hydroxyl) are ester radicals. The esterlinked saturated polyols are structurally represented as ##STR1## whereR and R' are organic residues which contain at least two hydroxylradicals and at least one ester link.

Examples of ester linked saturated polyols include Niax PCP0200 andPCP0240 both available from Union Carbide and having respectivemolecular weights of approximately 530 and 2000. Both of the foregoingcompounds are diols. Niax PCP0300 also available from Union Carbide is aCaprolactone-ester triol having approximate molecular weight of 540.Niax PCP0310 also available from Union Carbide is a Caprolactone-estertriol having a molecular weight of approximately 900.

The ether linked saturated polyols of the present invention includecompounds such as diethylene glycol and triethylene glycol bothavailable from Fisher. Further ether linked saturated polyols useful inthe present invention include the Polymeg Q0650, Q0100, and Q0200 all ofwhich are ether diols available from Quaker having a respectivemolecular weight of approximately 650, 1000 and 2000. Pluarcol P1010having an approximate molecular weight of 1050 available from Wyandotteis an example of a polypropylene oxide ether linked diol useful in thepresent invention. Similar Wyandotte products useful as saturatedpolyols in the present invention include Pluracol TP440 and 150 whichare propylene oxide ether linked triols having respective molecularweights of approximately 425 and 1560. In similar fashion PluaracolGP3030 is another saturated polyol suitable for the present inventionavailable from Wyandotte. The foregoing material is a glycerinepolypropylene ether linked triol having an approximately molecularweight of 2900.

Additional Pluracols useful in the present invention include PluarcolPEP450 which is a pentaerythritol polypropylene oxide ether linkedtetrol having a molecular weight of 405 and Pluracol 493 an ether linkedtetrol having a molecular weight of approximately 3630.

Ester and ether linked saturated polyols suitable in the presentinvention are described structurally as ##STR2## where R, R' and R" areorganic residues containing at least two hydroxyl radicals and at leastone ester and one ether linkage.

The following exemplify the present invention.

EXAMPLE I

The manufacture of the formyloctadecanol of the present invention isaccomplished by charging a 1 liter Magne Drive, 316 SS autoclave with606 grams (2.26 moles) of oleyl alcohol, 3.01 grams of 5% rhodium onalumina and 3 grams (9.68 moles) of triphenylphosphite.

The autoclave is sealed and pressurized to 10 atmospheres with nitrogenunder stirring and then vented to atmospheric pressure. The nitrogenpurge is repeated twice more to ensure removal of any oxygen present inthe autoclave.

The autoclave is then pressurized a third time with premixed carbonmonoxide and hydrogen gas in a 1 to 1 molar ratio to 68 atmospheres atwhich point heating is started. Stirring is manually controlled at 1250rps and the uptake of the mixture of the gases starts at about 100degrees C.

The reaction conditions are then maintained at a temperature of 130degrees C. and the gas pressure at 70 to 75 atmospheres.

The reaction is substantially complete after 4.6 hours and is determinedby the cessation of the gas uptake. The confirmation of completeness ofthe reaction is obtained by sampling the mixture and determining throughgas chromatograph analysis that there is less than 1% of the startingalcohol in the mixture.

The reaction mixture is then cooled to 75 degrees C., vented toatmospheric pressure and purged twice with nitrogen. The contents of theautoclave are then discharged at 75 degrees C. under nitrogen pressurethrough a pressure filter. The yield of the formyloctadecanol is greaterthan 90%. Atomic absorption analysis of the filtered product showed 244ppm of rhodium.

The reaction may be modified by using triphenylphosphine in place of thetriphenylphosphite. Alternatively the oleyl alcohol may be substitutedfor by linoleyl or linolenyl alcohol. The reaction temperature may alsobe lowered to 90 degrees C. at which point the reaction takes asubstantially longer period of time to proceed. As a second alternativethe reaction temperature can be raised to about 170 degrees C. and thereaction time considerably lowered. However, some decomposition of theend product may occur above the 170 degree figure so it should not beexceeded.

In similar fashion the mixture of carbon monoxide and hydrogen may bevaried as previously described in the Detailed Description of theInvention and may also be varied between about 20 and 500 atmospheres ofpressure. The lower end of the pressure range of course slows thereaction rate down while the higher pressure condition increases thereaction but also increases the probability that some of the startingalcohol will be saturated by the hydrogen.

EXAMPLE II

5.26 moles (1570 grams) of the formyloctadecanol obtained from Example Iis charged into a 5 liter glass round bottom reaction flask equippedwith a heat exchanger coil, thermocouple, stirrer, addition inlet,reflux condensor and combination glass electrode. A further reactioncharge of 695 grams (12.87 moles) of a 55.6% formaldehyde in methanolsolution is added under a nitrogen blanket. A 40% solution of sodiumhydroxide is made by dissolving 245.7 grams (5.95 moles) of sodiumhydroxide in 368 grams of water under a nitrogen blanket. The causticsolution is added to a charge tank and connected to the feed side of ametering pump.

The reaction mixture is heated to 30 degrees C. and the causticcarefully added by means of a metering pump with stirring to adjust thepH to about 10.9. After about forty minutes at 30 degrees C. theaddition of the 40% caustic solution is started at a rate of 9.65milliliters per minute and the temperature of the reaction is increasedto 60 degrees C. The addition of caustic required about 45 minutes andthe reaction temperature was maintained at 60 degrees C. Gaschromatograph analysis of a sample taken at this time indicated that thereaction was complete and that the gem-bis(hydroxymethyl) alcoholcorresponding to the formyloctadecanol is formed.

The reaction is held for an additional 20 minutes at 60 degrees C. Gaschromatograph analysis of a sample taken at this time indicated that thereaction was complete and that the gem-bis(hydroxymethyl) alcoholcorresponding to the formyloctadecanol is formed.

The reaction is held for an additional 20 minutes at 60 degrees C. aftercompletion of the caustic addition. The stirring is then stopped and thelower aqueous phase (816 grams) was allowed to separate.

After washing of the crude gem-bis(hydroxymethyl) octadecanol and itsdrying vacuum the amount recovered is 1711 grams corresponding to ayield of greater than 90%.

Alternatively linoleyl or linolenyl alcohol derivatives of Example I maybe employed under similar conditions. The reaction temperature for theproduction of the bishydroxymethyloctadecanol may also be convenientlyvaried between 0 degrees C. and 100 degrees C. as previously discussed.

An alternative method of obtaining the bishydroxymethyloctadecanol is touse 6.43 moles of the 55.6% formaldehyde solution thereby yielding thecorresponding hydroxymethyl formyloctadecanol as an isolatable product.This material is then reduced through catalytic hydrogenation withcopper chromite or through the use of lithium aluminum hydride to givethe gem-bis(hydroxymethyl)octadecanol.

EXAMPLE III

A polyurethane casting is prepared by reacting 58 parts of the9,9)10,10)-bis(hydroxymethyl)octadecanol with 59 parts ofisophorone-diisocyanate. The mixture is warmed slightly to promotehomogeneity. A small portion of dibutyltindilaurate (0.46 parts) isadded to the foregoing mixture with rapid stirring whereupon the mixturesets into a clear, colorless, hard solid in about one minute. A distinctadvantage in the products of the present invention is that they tend tocure into clear, colorless solids.

EXAMPLE IV

A one shot elastomer is prepared by combining9,9(10,10-bis(hydroxymethyl)octadecanol and 9(10) hydroxymethyloctadecanol (9:1 ratio) and a 10% stoichiometric excess of an 80:20mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate fortwo minutes at room temperature during which time the exothermicreaction raises the temperature to 100 degrees C. At this time theproduct is poured into a mold and is cured for sixteen hours at 100degrees C. This product was found to be an extremely hard materialhaving a Shore D hardness of 82 and is a crystal clear solid having agreat impact resistance.

Substantially similar results may be obtained in the above reaction bysubstituting the higher molecular weight gem-bis(hydroxymethyl) alcoholspreviously described at the above proportions with the 9(10)hydroxymethyl octadecanol.

EXAMPLE V

A polyurethane elastomer of the present invention is produced from amixture comprising 90% by weight of 9,9(10,10)-bis(hydroxymethyl)octadecanol and 10% by weight of 9(10) hydroxymethyl octadecanol throughreaction with a 10% stoichiometric excess of isophorone-diisocyanate forone hour at 80 degrees C. followed by pouring the reaction mixture intoa mold. The molded specimen is further cured for sixteen hours at 100degrees C. and thereafter removed from the mold. The polyurethaneelastomer so obtained is extremely hard having a Shore D hardness of 76and appears as a crystal clear solid which did not fracture uponstriking soundly with a hammer.

Substantially similar results may be obtained in the above reaction bysubstituting the higher molecular weight gem-bis(hydroxymethyl) alcoholspreviously described at the above proportions with the 9(10)hydroxymethyl octadecanol.

What is claimed is:
 1. A mixture of a diol (a) and a alcohol (b) of theformula:(a) H(CH₂)_(h) CH(CH₂ OH)(CH₂)_(k) CH₂ OHand (b) CH₃ (CH₂)_(m)[C(CH₂ OH)₂ ]_(n) (CH₂)_(p) [C(CH₂ OH)₂ ]_(q) (CH₂)_(r) [C(CH₂ OH)₂]_(s) (CH₂)_(t) CH₂ OHand mixtures thereof wherein n plus q plus s areintegers the sum of which is from 1 to 3; k and t are 3 or greater; n,q, and s are 0 or 1; m through t are integers the sum of which is from12 to 20; and, h plus k are non-zero integers the sum of which is from12 through
 20. 2. The composition of claim 1 wherein the sum of h plus kis from 14 to
 18. 3. The composition of claim 1 wherein the sum of mthrough t is from 14 to
 18. 4. The composition of claim 1 wherein q is 1and n and s are each
 0. 5. The composition of claim 1 wherein m, h, kand t are each 4 or greater.
 6. The composition of claim 1 wherein thediol is 9(10)-hydroxymethyl octadecanol.
 7. The composition of claim 1wherein the alcohol is 9,9(10,10)-bishydroxymethyloctadecanol.
 8. Thecomposition of claim 1 wherein the alcohol is a 9,9(10,10); 12,12(13,13)di[bis(hydroxymethyl)]octadecanol.
 9. The composition of claim 1 whereinthe alcohol is a 9,9(10,10); 12,12(13,13); 15,15(16,16)tri[bis(hydroxymethyl)] octadecanol.
 10. The composition of claim 1wherein the weight ratio of the alcohol to the diol is from about 1:2 toabout 100:1.
 11. The composition of claim 1 wherein n,p, r and s are 0;q is 1 and m plus t is from 11 through 19.